The present invention relates to a simplified method of printing cellulosic fibre materials in which a separate fixing process, such as the steaming of the printed fibre material, is superfluous. The method is simplified by the use of certain reactive dyes which are distinguished by at least three fibre-reactive groups, at least two of the said fibre-reactive groups being halotriazinyl radicals and at least one being especially of the vinylsulfonyl type. The present invention relates also to the novel reactive dyes.
Methods of printing cellulosic fibre materials have been known for a long time. The class of the reactive dyes has been successful in the face of the ever increasing demands in terms of colour fastness. In printing procedures on cellulose fibres that employ reactive dyes, use is made of the particularly stable covalent binding of the dyes to the hydroxy groups of the fibres. The binding of the reactive dyes to the fibres (fixing) is carried out in alkaline medium and requires treatment of the printed fibre material in a separate fixing process, which is usually carried out with saturated steam at relatively high temperatures (steaming), in order to achieve uniform and optimum fixing of the dye. In the hitherto known methods, such a treatment requires an additional device in which the necessary fixing heat and the steam are generated. There is accordingly a need for a simplified printing method that can be used on an industrial scale in which the additional process step of fixing the dye does not need to be carried out and in which uniform and optimum fixing is, for example, achieved directly on drying the printed fibre material. The advantage of such a simplified method is especially that expenditure in terms of time and cost is distinctly lower than in the case of the hitherto customary printing methods, since it is possible to omit the additional process step of fixing the dye and thus dispense with the additional fixing device.
The present invention accordingly relates to a method of printing cellulosic fibre materials in which the fibre material is brought into contact with reactive dyes of formula: 
wherein
A is the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore,
R1, R2 and R3 are each independently of the others hydrogen or unsubstituted or substituted C1-C4alkyl,
X1 and X2 are halogen,
B is an organic bridging member,
T is a reactive radical of formula: 
R4 is hydrogen, C1-C4alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or by cyano, or a radical 
xe2x80x83wherein R5 is as defined hereinbelow,
R5 is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C1-C4alkoxycarbonyl,
C1-C4alkanoyloxy, carbamoyl or a group xe2x80x94SO2xe2x80x94Y,
R6 is hydrogen or C1-C4alkyl,
alk and alk1 are each independently of the other linear or branched C1-C6alkylene,
arylene is an unsubstituted or sulfo-, carboxy-, hydroxy-, C1-C4alkyl-, C1-C4alkoxy- or halo-substituted phenylene or naphthylene radical,
Y is vinyl or a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U and U is a leaving group,
Y1 is a group xe2x80x94CH(Hal)-CH2(Hal) or xe2x80x94C(Hal)xe2x95x90CH2, wherein Hal is chlorine or bromine,
W is a group xe2x80x94SO2xe2x80x94NR6xe2x80x94, xe2x80x94CONR6xe2x80x94 or xe2x80x94NR6COxe2x80x94, wherein R6 is as defined hereinabove,
Q is a radical xe2x80x94Oxe2x80x94 or xe2x80x94NR6xe2x80x94, wherein R6 is as defined hereinabove,
n is the number 0 or 1, and
V1 and V2 are each independently of the other N, Cxe2x80x94H, Cxe2x80x94Cl or Cxe2x80x94F,
and the fixing of the printed fibre material is carried out without an additional fixing process step.
Within the context of the present invention, xe2x80x9can additional fixing process stepxe2x80x9d denotes the treatment of the fibre material, after the printing and after the drying immediately subsequent thereto, in a separate fixing device at relatively high temperatures, which step is usually carried out in the presence of saturated steam (steaming).
According to the invention, the fixing of the dye on the fibre material has already been achieved immediately after the printing and also the drying of the fibre material, which is to be carried out anyway.
Preferably, the method according to the invention is carried out industrially on a large scale.
As alkyl radicals in the reactive dye of formula (1), the radicals R1, R2 and R3 are straight-chain or branched. The alkyl radicals may be further substituted, for example by hydroxy, sulfo, sulfato, cyano or carboxy. The following radicals may be mentioned as examples: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, and the corresponding radicals substituted by hydroxy, sulfo, sulfato, cyano or carboxy. Preferred substituents are hydroxy, sulfo or sulfato, especially hydroxy or sulfato and preferably hydroxy.
Preferably, R1 is hydrogen or C1-C4alkyl, especially hydrogen.
R2 and R3 are preferably each independently of the other hydrogen, or C1-C4alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy. According to one embodiment of interest, one of the radicals R2 and R3 is C1-C4alkyl substituted by hydroxy, sulfo, sulfato, cyano or by carboxy, especially by hydroxy, and the other of the radicals R2 and R3 is hydrogen or C1-C4alkyl, especially hydrogen.
Especially preferably, R2 and R3 are each independently of the other hydrogen or C1-C4alkyl, especially hydrogen.
X1 and X2 are, for example, chlorine, fluorine or bromine.
X1 and X2 are preferably each independently of the other chlorine or fluorine. Especially preferably, one of the radicals X1 and X2 is fluorine and the other is chlorine, or X1 and X2 are both fluorine. More especially, one of the radicals X1 and X2 is fluorine and the other is chlorine.
V1 and V2 are preferably N.
The organic bridging member B may be, for example, an aliphatic, cycloaliphatic, aromatic or araliphatic bridging member.
As an aliphatic bridging member, B is, for example, a straight-chain or branched C2-C12-alkylene radical, especially a C2-C6alkylene radical, that may be interrupted by 1, 2 or 3 members from the group xe2x80x94NHxe2x80x94, xe2x80x94N(CH3)xe2x80x94 and especially xe2x80x94Oxe2x80x94 and that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy. Hydroxy, sulfo or sulfato, especially hydroxy or sulfato, are preferred as substituents of the alkylene radicals mentioned for B.
As aliphatic bridging members for B there come into consideration also, for example, C5-C9-cycloalkylene radicals, especially cyclohexylene radicals. The said cycloalkylene radicals may be unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxy, especially by C1-C4alkyl. As aliphatic bridging members for B there may also be mentioned methylenecyclohexylene, ethylenecyclohexylene and methylenecyclohexylenemethylene radicals unsubstituted or substituted in the cyclohexylene ring by C1-C4alkyl, especially methyl.
For the radical of formula 
there comes into consideration, for example, also a radical of formula 
wherein alk is C1-C4alkylene, for example ethylene.
As an aromatic bridging member, B is, for example, unsubstituted or C1-C4alkyl-, C1-C4alkoxy-, C2-C4alkanoylamino-, sulfo-, halo- or carboxy-substituted C1-C6alkylenephenylene, for example methylenephenylene, C1-C4alkylenephenylene-C1-C4alkylene, for example methylenephenylenemethylene, or phenylene, or a radical of formula: 
wherein the benzene rings I and II are unsubstituted or substituted by C1-C4alkyl, C1-C4-alkoxy, C2-C4alkanoylamino, sulfo, halogen or by carboxy and L is a direct bond or a C2-C10-alkylene radical that may be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridging member of formula xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Nxe2x95x90Nxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94SO2xe2x80x94, xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94SO2xe2x80x94. As an aromatic bridging member, B is preferably phenylene that may be substituted as indicated above. Preferably, the aromatic bridging members mentioned for B are unsubstituted or sulfo-substituted.
Examples of aromatic bridging members B are 1,3-phenylene, 1,4-phenylene, 4-methyl-1,3-phenylene, 4-sulfo-1,3-phenylene, 3-sulfo-1,4-phenylene, 3,6-disulfo-1,4-phenylene, 4,6-disulfo-1,3-phenylene, 3,7-disulfo-1,5-naphthylene, 4,8-disulfo-2,6-naphthylene, 2,2xe2x80x2-disulfo-4,4xe2x80x2-diphenylene, 4,4xe2x80x2-phenyleneurea-2,2xe2x80x2-disulfonic acid and 2,2xe2x80x2-disulfo-4,4xe2x80x2-stilbenylene.
B is preferably a C2-C12alkylene radical that may be interrupted by 1, 2 or 3 members from the group xe2x80x94NHxe2x80x94, xe2x80x94N(CH3)xe2x80x94 or xe2x80x94Oxe2x80x94 and that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy;
an unsubstituted or C1-C4alkyl-, C1-C4alkoxy-, C2-C4alkanoylamino-, sulfo-, halo- or carboxy-substituted C5-C9cycloalkylene radical, C1-C6alkylenephenylene radical or phenylene radical;
or the radical of formula 
xe2x80x83is a radical of formula 
B is especially a C2-C12alkylene radical that may be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy, or is a phenylene radical that is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4-alkanoylamino, sulfo, halogen or by carboxy.
B is more especially a C2-C12alkylene radical, especially a C2-C6alkylene radical, for example 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,5-pentylene, 3,5-pentylene, 1,6-hexylene, 2,5-hexylene, 4,6-hexylene or a radical of formula: 
that may be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and that is unsubstituted or substituted by hydroxy or by sulfato, but preferably that is not interrupted by xe2x80x94Oxe2x80x94.
Of particular importance as bridging members B are those of formula xe2x80x94CH2xe2x80x94CH(R7)xe2x80x94 wherein R7 is C1-C4alkyl, especially methyl, and especially 1,2-propylene.
Of particular importance also, as the radical 
is a radical of formula: 
When Y is a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U, the leaving group U may be, for example, xe2x80x94Cl, xe2x80x94Br, xe2x80x94F, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, OPO3H2, xe2x80x94OCOxe2x80x94C6H5, OSO2xe2x80x94C1-C4alkyl or xe2x80x94OSO2xe2x80x94N(C1-C4alkyl)2. Preferably, U is a group of formula xe2x80x94Cl, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OCOxe2x80x94C6H5 or xe2x80x94OPO3H2, especially xe2x80x94Cl or xe2x80x94OSO3H and more especially xe2x80x94OSO3H.
Y is preferably vinyl, xcex2-chloroethyl, xcex2-sulfatoethyl, xcex2-thiosulfatoethyl, xcex2-acetoxyethyl, xcex2-phenoxyethyl or xcex2-phosphatoethyl and especially xcex2-sulfatoethyl or vinyl.
Hal is preferably bromine.
alk and alk1 are each independently of the other, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene or a branched isomer thereof. alk and alk1 are each independently of the other preferably a C1-C4alkylene radical and especially an ethylene or propylene radical.
Preferred meanings of arylene are an unsubstituted or sulfo-, methyl-, methoxy- or carboxy-substituted 1,3- or 1,4-phenylene radical and especially an unsubstituted 1,3- or 1,4-phenylene radical.
R4 is preferably hydrogen, C1-C4alkyl or a radical of formula 
wherein R5, Y and alk each have the definitions and preferred meanings given hereinabove. R4 is especially hydrogen, methyl or ethyl and more especially hydrogen.
R5 is preferably hydrogen.
R6 is preferably hydrogen, methyl or ethyl and especially hydrogen.
The variable Q is preferably xe2x80x94NHxe2x80x94 or xe2x80x94Oxe2x80x94 and especially xe2x80x94Oxe2x80x94.
W is preferably a group of formula xe2x80x94CONHxe2x80x94 or xe2x80x94NHCOxe2x80x94, especially a group of formula xe2x80x94CONHxe2x80x94.
The variable n is preferably the number 0.
Preferred reactive radicals T of formulae (2a) to (2f) are those wherein R4, R5 and R6 are each hydrogen, Q is the radical xe2x80x94NHxe2x80x94 or xe2x80x94Oxe2x80x94, W is a group xe2x80x94CONHxe2x80x94, alk and alk1 are each independently of the other ethylene or propylene, arylene is unsubstituted or methyl-, methoxy-, carboxy- or sulfo-substituted phenylene, Y is vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl, especially vinyl or xcex2-sulfatoethyl, Y1 is xe2x80x94CHBrxe2x80x94CH2Br or xe2x80x94CBrxe2x95x90CH2 and n is the number 0, the radicals of formulae (2c) and (2d) being especially preferred.
T is more especially a group of formula: 
especially (2cxe2x80x2), in which formulae Y has the definitions and preferred meanings given hereinabove.
An especially important reactive radical T is the radical of formula: 
wherein Y is vinyl or xcex2-sulfatoethyl.
When A is the radical of a monoazo, polyazo or metal complex azo chromophore, the following, especially, come into consideration:
chromophore radicals of a monoazo or disazo dye of formula
Dxe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)uxe2x80x94Kxe2x80x94xe2x80x83xe2x80x83(4)
or
xe2x80x94Dxe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)uxe2x80x94Kxe2x80x83xe2x80x83(5),
xe2x80x83wherein D is the radical of a diazo component of the benzene or naphthalene series, M is the radical of a central component of the benzene or naphthalene series, K is the radical of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series and u is the number 0 or 1, and wherein D, M and K may carry substituents customary for azo dyes, for example C1-C4alkyl or C1-C4alkoxy each unsubstituted or further substituted by hydroxy, sulfo or by sulfato; halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, carboxy, sulfomethyl, C2-C4alkanoylamino; benzoylamino unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or by sulfo; phenyl unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxy or by sulfo; and fibre-reactive radicals. There also come into consideration the metal complexes derived from the dye radicals of formulae (4) and (5), such dye radicals being especially those of a 1:1 copper complex azo dye or 1:2 chromium complex azo dye of the benzene or naphthalene series, wherein the copper or chromium atom, as the case may be, is bonded to a metallisable group in the ortho position on both sides of the azo bridge.
When the chromophore radicals of formula (4) or (5) carry a reactive radical, the reactive radical may be, for example, of formula
xe2x80x83xe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(6a),
xe2x80x94CONHxe2x80x94(CH2)mxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(6b),
xe2x80x94CONHxe2x80x94(CH2)lxe2x80x94Oxe2x80x94(CH2)mxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(6c),
xe2x80x94(O)pxe2x80x94(CH2)qxe2x80x94CONHxe2x80x94(CH2)mxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(6d),
xe2x80x94NHxe2x80x94COxe2x80x94CH(Hal)-CH2(Hal)xe2x80x83xe2x80x83(6e),
xe2x80x94NHxe2x80x94COxe2x80x94C(Hal)xe2x95x90CH2xe2x80x83xe2x80x83(6f)
or 
in which formulae Y and Hal each have the definitions and preferred meanings given hereinabove, T1 independently has the definitions and preferred meanings given hereinabove for T, X2xe2x80x2 independently has the definitions and preferred meanings given hereinabove for X2, R3xe2x80x2 independently has the definitions and preferred meanings given hereinabove for R3, p is the number 0 or 1 and l, m and q are each independently of the others an integer from 1 to 6. Preferably, p is the number 0,l and m are each independently of the other 2 or 3 and q is the number 1, 2, 3 or 4.
When the chromophore radicals of formula (4) or (5) carry a reactive radical, the reactive radical preferably corresponds to the above formula (6a) or (6g).
Preferably, the chromophore radicals of formula (4) or (5) do not carry a reactive radical.
Especially preferred radicals of a monoazo or disazo chromophore A are as follows: 
in which formulae (R8)0-3 denotes from 0 to 3 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy, halogen, carboxy and sulfo, 
wherein (R9)0-4 denotes from 0 to 4 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4alkyl, C1-C4alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo, 
in which formulae R10 is hydrogen, C1-C4alkanoyl, benzoyl or a halotriazinyl radical of the above-indicated formula (6g), 
in which formulae (R11)0-3 denotes from 0 to 3 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy, halogen, carboxy and sulfo, 
wherein R12 and R14 are each independently of the other hydrogen, C1-C4alkyl or phenyl and R13 is hydrogen, cyano, carbamoyl or sulfomethyl, 
wherein (R15)0-2 denotes from 0 to 2 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy, halogen, carboxy and sulfo; and Y is as defined hereinabove, 
wherein (R16)0-2 denotes from 0 to 2 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy, halogen, carboxy and sulfo, and Y has the definitions given hereinabove, 
in which formulae (R8)0-3 denotes from 0 to 3 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy, halogen, carboxy and sulfo, (R8xe2x80x2)0-3 denotes from 0 to 3 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy, acetylamino, halogen, carboxy, sulfo, C1-C4hydroxyalkoxy and C1-C4sulfatoalkoxy, (R9)0-3 denotes from 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4alkyl, C1-C4alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo, (R10xe2x80x2)0-3 denotes from 0 to 3 identical or different substituents from the group C1-C4alkyl, C1-C4alkoxy, halogen, carboxy and sulfo, and Y is as defined hereinabove.
The radicals of formulae (7a) to (7s) may carry in the phenyl or naphthyl rings, as a further substituent, also a radical of formula xe2x80x94SO2Y, wherein Y is as defined hereinabove. Preferably they do not contain a radical of formula xe2x80x94SO2Y.
The radical of a formazan dye A is preferably a dye radical of formula 
wherein the benzene nuclei do not contain any further substituents or are further substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylsulfonyl, halogen or carboxy.
As a radical of a phthalocyanine dye, A is preferably a radical of formula: 
wherein Pc is the radical of a metal phthalocyanine, especially the radical of a copper or nickel phthalocyanine; R is xe2x80x94OH and/or xe2x80x94NR18R19; R18 and R19 are each independently of the other hydrogen or unsubstituted or hydroxy- or sulfo-substituted C1-C4alkyl; R17 is hydrogen or C1-C4alkyl; E is a phenylene radical unsubstituted or substituted by C1-C4alkyl, halogen, carboxy or by sulfo or is a C2-C6alkylene radical; and k is from 1 to 3. R18 and R19 are preferably hydrogen. E is preferably a phenylene radical unsubstituted or substituted by C1-C4alkyl, halogen, carboxy or by sulfo. Pc is preferably the radical of a copper phthalocyanine.
As a radical of a dioxazine dye, A is, for example, a radical of formula: 
wherein Exe2x80x2 is a phenylene radical unsubstituted or substituted by C1-C4alkyl, halogen, carboxy or by sulfo or is a C2-C6alkylene radical, r, s, v and vxe2x80x2 are each independently of the others the number 0 or 1 and Y is as defined hereinabove. Preferably, Exe2x80x2 is C2-C4alkylene or unsubstituted or sulfo-substituted 1,3- or 1,4-phenylene, r is the number 1, s is the number 0, v is the number 1 and vxe2x80x2 is the number 0 or 1.
As a radical of an anthraquinone dye, A is preferably a radical of formula: 
wherein G is a phenylene radical unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxy or by sulfo, or is a cyclohexylene, phenylenemethylene or C2-C6alkylene radical, each of which preferably contains at least 2 sulfo groups. G is preferably a phenylene radical unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxy or by sulfo.
A is especially a monoazo or disazo chromophore radical of the above-indicated formula (7a), (7b), (7d), (7e), (7f), (7k), (7o), (7q) or (7t), a formazan radical of the above-indicated formula (8b), or an anthraquinone radical of the above-indicated formula (11).
In the meanings given for the variables, C1-C4alkyl is generally methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl. C1-C4Alkoxy is generally methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy. Halogen is generally, e.g., fluorine, chlorine or bromine. Examples of C1-C4alkoxycarbonyl are methoxycarbonyl and ethoxycarbonyl. Examples of C1-C4alkanoyl are acetyl, propionyl and butyryl. Examples of C2-C4alkanoylamino are acetylamino and propionylamino. Examples of C1-C4hydroxyalkoxy are hydroxymethoxy, xcex2-hydroxyethoxy and xcex2- and xcex3-hydroxypropoxy. Examples of C1-C4sulfatoalkoxy are sulfatomethoxy, xcex2-sulfatoethoxy and xcex2- and xcex3-sulfatopropoxy.
The reactive dyes of formula (1) contain at least one, preferably at least two and especially from 2 to 8, sulfo groups, each of which is either in the form of its free acid or preferably a salt thereof. As salts there come into consideration, for example, the alkali metal, alkaline earth metal and ammonium salts, salts of an organic amine and mixtures thereof. As examples there may be mentioned sodium, lithium, potassium and ammonium salts, the salt of mono-, di- or tri-ethanolamine and Na/Li and Na/Li/NH4 mixed salts.
The reactive dyes of formula (1) can be obtained in a manner known per se, such as in the manner described, for example, in U.S. Pat. No. 5,989,297, for example as follows:
an amino compound of formula
Axe2x80x94NHxe2x80x94R1xe2x80x83xe2x80x83(12),
a diamine of formula
R2xe2x80x94HNxe2x80x94Bxe2x80x94NHxe2x80x94R3xe2x80x83xe2x80x83(13),
a compound of formula
Txe2x80x94Hxe2x80x83xe2x80x83(14)
xe2x80x83and
a compound of formula 
xe2x80x83are reacted with one another in any sequence, in which formulae B, A, R1, R2, R3, T, V1, V2, X1 and X2 are each as defined hereinabove. One process variant comprises condensing one of the compounds of formulae (12) and (14) first of all with a compound of formula (15a) or (15b), condensing the condensation product with a diamine of formula (13) and reacting the resulting reaction product with the other compound of formula (12) or (14) which has been condensed beforehand with the compound of formula (15a) or (15b).
The condensation reactions between the compounds of formulae (12), (13), (14), (15a) and (15b) are generally carried out analogously to known procedures, usually in aqueous solution at temperatures of, for example, from 0 to 50xc2x0 C. and a pH value of, for example, from 4 to 10. The compounds of formulae (12), (13) and (14), as well as the heterocyclic halogen compounds of formulae (15a) and (15b), are known or can be prepared analogously to known compounds.
The end product may optionally in addition be subjected to a conversion reaction. Such a conversion reaction is, for example, the conversion of a vinylatable reactive group present in T into its vinyl form by treatment with dilute sodium hydroxide solution, for example the conversion of the xcex2-sulfatoethylsulfonyl or xcex2-chloroethylsulfonyl group into the vinylsulfonyl radical. Such reactions are known per se.
In the method according to the invention there are used for the printing, for example, pastes, that is to say aqueous solutions thickened and adjusted to the desired consistency by a thickener.
There may be used as thickeners the customary thickeners of natural or synthetic origin suitable for reactive printing, e.g. alginate thickeners, starch ethers or locust bean flour ethers, cellulose derivatives, e.g. cellulose ethers, such as methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethylcellulose, carboxyethylcellulose or cyanoethylcellulose, or a cellulose ester, e.g. acetylcellulose. Preference is given to the use in the print pastes of sodium alginate alone or in admixture with modified cellulose, especially with preferably from 20 to 25% by weight carboxymethylcellulose.
The amount of thickener in the print paste can vary within wide limits according to the desired viscosity. Preferably, the amount of thickener present in the print paste is from 5 to 100 g/kg of print paste, especially from 10 to 80 g/kg of print paste, more especially from 10 to 60 g/kg of print paste.
The viscosity of the print paste is generally from 1000 to 20 000 mPa s. Preference is given to the use of print pastes having a viscosity of from 2500 to 15 000 mPa s, especially from 4000 to 6000 mPa s.
The print pastes may comprise fixing alkalis for the purpose of fixing the reactive dyes. As compounds having an alkaline reaction there are used, for example, sodium carbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, borax, aqueous ammonia or alkali donors, e.g. sodium chloroacetate or sodium formate. It is also possible to use as fixing alkali a mixture of water glass and a 25% aqueous sodium carbonate solution. The pH value of the additives comprising fixing alkali is generally from 7.5 to 13.2, preferably from 8.5 to 12.5. For the preparation of the print paste, the amount of fixing alkali is so selected that the pH value of the ready-to-use print paste is generally in the alkaline range, preferably in the range from 7.5 to 12.
Print pastes that do not comprise fixing alkali can be applied according to the so-called two-phase printing method, in which the fibre material is first printed with a print paste without alkali or alkali donor, and the printed fibre material is dried and then treated with an optionally thickened aqueous liquor comprising the fixing alkali. Alternatively, the fibre material to be printed can first be treated with an aqueous alkali liquor and then the treated and optionally dried fibre material printed with a print paste that does not comprise alkali or alkali donor.
The print paste may also comprise, in addition to the reactive dyes and thickeners, further customary additives, e.g. preservatives, sequestering agents, emulsifiers, water-insoluble solvents, oxidising agents, reduction inhibitors, antifoams or de-aerators.
There come into consideration as preservatives especially formaldehyde-yielding agents, e.g. paraformaldehyde and trioxane, especially aqueous, for example 30 to 40% by weight, formaldehyde solutions; as sequestering agents, for example, nitrilotriacetic acid sodium salt, ethylenediaminetetraacetic acid sodium salt, especially sodium polymetaphosphate, more especially sodium hexametaphosphate; as emulsifiers especially adducts of an alkylene oxide and a fatty alcohol, more especially an adduct of oleyl alcohol and ethylene oxide; as water-insoluble solvents high-boiling, saturated hydrocarbons, especially paraffins having a boiling range of approximately from 160 to 210xc2x0 C. (so-called white spirits); and as oxidising agents, for example, an aromatic nitro compound, especially an aromatic mono- or di-nitro-carboxylic acid or -sulfonic acid, which is optionally present in the form of an alkylene oxide adduct, especially a nitrobenzenesulfonic acid.
As reduction inhibitors there come into consideration, for example, aromatic nitro compounds, especially salts of aromatic mono- or di-nitro-carboxylic acids or -sulfonic acids, which are optionally in the form of alkylene oxides, especially alkali metal salts of a nitro-benzenesulfonic acid, e.g. 4-nitrobenzenesulfonic acid sodium salt. The reduction inhibitor is preferably used in an amount of from 0.1 to 4% by weight, especially from 0.8 to 2% by weight, based on the total weight of the finished print paste.
There may be used as de-aerator any commercially available de-aerator provided that it does not adversely affect the rheological properties of the print paste. Preference is given, on account of their good anti-foaming properties, to low-silicone oil or silicone oil-free de-aerators, which generally contain from 0 to 5% by weight of a conventional silicone oil. Of prime interest are de-aerators that comprise as active substance a higher alcohol, such as 2-ethyl-n-hexanol or 2-hexyldecanol, or a mixture thereof with high-boiling hydrocarbon mixtures, and that comprise silicone oils in the amount indicated above. The print paste comprises the de-aerator in an amount of, for example, from 0 to 5% by weight, preferably from 0.1 to 1% by weight, based on the total weight of the finished print paste.
The print pastes may comprise as further additives solubilisers, such as urea, xcex5-caprolactam, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, pentaerythritol, acetin (mixture of glycol mono-, di- and tri-acetate) or dicyandiamide.
When printing on fibre materials, the print paste is applied directly to the fibre material over the entire surface or over parts thereof, the printing machines used advantageously being of customary construction, e.g. gravure printing machines, rotary screen printing machines and flat screen printing machines. The method according to the invention is used especially advantageously in screen printing.
As cellulosic fibre materials there come into consideration materials that consist wholly or partially of cellulose. Examples include natural fibre materials, such as cotton, linen and hemp, regenerated fibre materials, e.g. viscose, polynosic and cuprammonium silk, and cellulosic blends, e.g. cotton/polyester materials. Mainly, woven fabrics, knitted fabrics or webs of such fibres are used.
The fibre material is advantageously dried after the printing procedure, preferably at temperatures of up to 180xc2x0 C., especially from 125 to 150xc2x0 C. A fixing process step customarily carried out subsequent thereto in order to complete the printing and fix the dye, such as steaming of the printed and dried fabric, is not necessary in the method according to the invention. After the printing procedure, the fibre material is preferably dried for from 30 to 120 seconds at from 125 to 150xc2x0 C., especially from 140 to 150xc2x0 C.
The printed and dried fibre material is washed off in conventional manner in order to remove unfixed dye. For that purpose the fibre material is treated, for example, at from 40xc2x0 C. to boiling temperature with water to which a soap or a synthetic detergent may optionally be added.
The prints on cellulosic fibre materials obtainable according to the method of the invention exhibit good allround properties; for example they have a high fibre-dye binding stability in both the acidic and the alkaline range, especially the acidic range, a good fastness to light, good wet-fastness properties, such as fastness to washing, to water, to sea water, to cross-dyeing and to perspiration, a good fastness to chlorine, fastness to rubbing, fastness to ironing and fastness to pleating, and are distinguished especially by sharp contours, a high tinctorial strength and brilliant colour shades. The degree of fixing is high and unfixed dye can readily be washed off, that is to say the soaping loss is very small.
Some of the reactive dyes of formula (1) are novel. The present invention accordingly relates also to reactive dyes of formula (1) indicated hereinabove wherein
B is C2-C12alkylene that may be interrupted by 1, 2 or 3 members from the group xe2x80x94NHxe2x80x94, xe2x80x94N(CH3)xe2x80x94 and xe2x80x94Oxe2x80x94 and that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy, and
A, R1, R2, R3, X1, X2, T, V1 and V2 have the definitions and preferred meanings given hereinabove,
with the exception of the dyes of formulae: 
As bridging member B in the reactive dyes according to the invention, preference is given to a C2-C12alkylene radical that may be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and that is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy.
As bridging member B in the reactive dyes according to the invention, preference is given especially to a C2-C12alkylene radical, especially a C2-C6alkylene radical, e.g. 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,5-pentylene, 3,5-pentylene, 1,6-hexylene, 2,5-hexylene, 4,6-hexylene or a radical of formula 
or 
which may be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxy or sulfato, but is preferably not interrupted by xe2x80x94Oxe2x80x94.
As bridging member B in the reactive dyes according to the invention, preference is given more especially to bridging members of formula xe2x80x94CH2xe2x80x94CH(R7)xe2x80x94 or xe2x80x94(R7)CHxe2x80x94CH2xe2x80x94, wherein R7 is C1-C4alkyl, especially methyl, and very especially to 1,2-propylene.
The novel reactive dyes can be obtained in a manner known per se, for example according to the process described above.
The present invention relates also to print pastes that comprise the reactive dyes of formula (1) according to the invention. The print pastes may also comprise, in addition to the reactive dyes according to the invention, to water and to a thickener, further additives, e.g. the additives described hereinabove. As thickeners there come into consideration, e.g., the thickeners described hereinabove.
The following Examples serve to illustrate the invention. Unless otherwise indicated, the temperatures are given in degrees Celsius, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to liters.